Patent GB-1090717-A (GB)
Title: Acryloyl phenols
IPC: C07C49/82
Filed: 1965-03-24
Abstract: Novel compounds of the Formula (I) wherein R represents a C1- 5 alkyl, halo-C1- 5 alkyl or cycloalkyl radical, or an unsubstituted or a halo- or C1- 5 alkyl substituted phenyl or phenyl-C1- 5 alkyl radical; each of R1 and R2 represents a hydrogen atom or a C1- 5 alkyl radical, each X represents a halogen atom or a C1- 5 alkyl radical or, when substituted on adjacent carbon atoms of the benzene nucleus, two X radicals may be linked to form a hydrocarbylene chain having 3 or 4 carbon atoms between its points of attachment to the benzene ring, and n represents an integer from 1 to 4 inclusive, with the proviso that when n represents 1 or 2, R1 represents a hydrogen atom and the acryloyl group is para to the hydroxy group, then R represents a halophenyl, (C1- 5 alkyl) phenyl, (C1- 5 alkyl) phenyl-C1- 5 alkyl or halophenyl-C1- 4 alkyl radical, are prepared by deaminating a compound of the Formula (II) or (III) (wherein -N(R3)2 represents a disubstituted amino group, R4 represents a hydrocarbyl radical, Y- represents a halogen anion, HA represents an acid capable of forming salts with amines and w represents 0 or 1), or by reacting a compound of the Formula (IV) (wherein X2 represents a halogen atom) with a dehydrohalogenation agent.  <FORM:1090717/C2/1> <FORM:1090717/C2/2> <FORM:1090717/C2/3> <FORM:1090717/C2/4> <FORM:1090717/C2/5> <FORM:1090717/C2/6> <FORM:1090717/C2/7> <FORM:1090717/C2/8> Amines of the Formula (II), which may be quaternized to give compounds of the Formula (III), may be prepared from the appropriate acylphenol of the Formula (V), according to the Mannich reaction with formaldehyde and a secondary amine salt of the formula HN(R3)2 HA.  Haloacylphenols of the Formula (IV) may be prepared by reacting the corresponding unhalogenated compounds of the Formula (VI) with a halogenating agent.  Alkenoylphenols of the Formula (Ia) are formed as by-products in the dehydrohalogenation of compounds of the Formula (IV).  Alkanoylphenols of the Formulae (V) and (VI) may be prepared by reacting the appropriate phenol ethers with alkanoyl halides in the presence of a Friedel-Craft catalyst and hydrolysing the resultant ethers, by reacting the appropriate phenols with alkanoyl halides and performing Fries re-arrangement on the resultant phenol esters, by reacting Grignard reagents of the formula R-CH2MgX3 or RCH (CHR1R2MgX3 (wherein X3 represents a halogen atom) with formylphenol ethers of the Formula (VII), oxidizing the resulting alkoxy substituted benzyl alcohols and converting the ether groups in the resultant alkanoylphenol ethers into free hydroxy groups, or by nitrating the appropriate alkanophenones, reducing the resultant 3-nitroalkanophenones to the corresponding 3-aminoalkanophenones and converting the latter to the desired 3-alkanoylphenols.ALSO:Therapeutic compositions with diuretic and saluretic properties which may take forms suitable for oral and parenteral administration comprise compounds of the formula <FORM:1090717/A5-A6/1> wherein R represents a C1-5 alkyl, halo-C1-5 alkyl or cycloalkyl radical or an unsubstituted or a halo- or C1-5 alkyl substituted phenyl or phenyl-C1-5 alkyl radical, each of R1 and R2 represents a hydrogen atom or a C1-5 alkyl group, each X represents a halogen atom or a C1-5 alkyl radical or, when substituted on adjacent carbon atoms of the benzene nucleus, two X radicals may be linked to form a hydrocarbylene chain having 3 or 4 carbon atoms between its points of attachment to the benzene ring, and n represents an integer of 1 to 4 inclusive together with a non-toxic pharmaceutical diluent, carrier or coating and, optionally, with an additional diuretic material or other therapeutic and/or nutritive agents.